Non-brittle, non-lustrous, oxidation resistant asphalt



United States PatentO NON-BRITTLE, NON-LUSTROUS, OXIDATION RESISTANT ASPHALT Edwin J. Barth, New York, N. Y.

No Drawing. Application March 5, 1957 Serial No. 643,950

2 Claims. (Cl; 106-232) It is well known to asphalt, paving technologists and engineers that the bituminous binder or asphalt (bitumen) in pavements and in roofing products deteriorate over a span of years to a marked degree.

Such deterioration is evidenced by road pavement break-up and in roofing felts, shingles, roof-coatings, and the like. In fact, all asphalts Whether used in roads, roofings, or for water-proofing lose with time their original resilience, softness and especially their adhesion the latter property of adhesion being the prime requisite for having used bitumens i. e. asphalts.

Road deterioration is, as commonly known, seen in the sand, stone or other inorganic or mineral aggregate breaking-up under trafiic and forming holes, cavities and erosion spots. The rain, snow and traffic are the ultimate factors to this attrition, and complete failure of the roadway. Loss of adhesion appears to be the underlying cause of this break-up of the road-way since the asphalt film, the binder on the stone or sand aggregate no longer cements the stone sand grains together.

Simlarly, in roofing products exposed also to the elements and often on inclined surfaces we find over the course of a few years, serious felt or shingle break-down exposing the roof below through small and then larger areas of dried out crumbly shingle felt, devoid of all adhesive bitumen.

The cause of this lack of adhesion is in all instances initiated and continuously maintained by a slow but constant rate of oxidation of the bituminous binder. We find as catalysts for this oxidation reaction that sunlight and water are quite efiicient inaccelerating the process of deterioration.

wholly dependent upon the state of solution of these three groups in one another, or how well the asphaltenes are dispersed in the oils, the dispersion medium by the group called resins, i. e. the peptizers or asphaltene stabilizers.

Where all these hydrocarbons are in partial to complete solution in one another, we have a first state or a colloidal system called a sol, which as is well known to rheologists has the quality of being tremendously adhesive.

In other bitumen, also well known and extensively used we find the asphaltenes have a larger particle size, and are in greater amount and are fairly well dispersed in the oils and are sufficiently adhesive for general use purposes, though rheological tests indicate the presence of a lessened degree of adhesivity than in the case of the sol condition described above. This is the sol-gel or second In the gel group we have a composition having a high I asphaltene content and quite often the asphaltenes are coarsely or ill dispersed in a somewhat deficient amount of resin peptizers and thus yield a rubbery asphalt. This condition produces a material of low adhesive properties.

Road or roof deterioration of asphalts appears, as already mentioned, to be due to a lack of adhesivity of the binder thereby allowing stones, sand, etc. in the road-way to loosen and result in pavement break-up.

It is believed from many tests made by asphalt chemists on bitumens extracted from new, aged and old pavements that an extensive oxidation takes place. This re-' sults in a continual and then final deterioration caused over the years in a bitumen of a sol nature wherein the asphaltene content has increased and the resin content has diminished with-loss of stickiness so that the composition lacks balance, adhesion and the proper amount of soft plasticizing oils which were originally present.

The deteriorated road asphalt has therefore over the years assumed a lowered degree of adhesivity found in many artificially oxidized or blown asphalts. mary, in the table below are presented three rheologically different types of asphalts and their colloidal composition. In this/table P. I. stands for the penetration index This deterioration results. in loss .of adhesiveness. done according to the Shell method and the melting point Water eventually tends .to wash away .the water-soluble is done by the ring and ball procedure.

Colloid Type or State Sol Sol-Gel Gel Rheological type Visco-elastie Elastic Newtonian (Calif) Mexican Venezuela Blown Blown 7 Venezuela Mexican Asphaltenes 4.6 22 1s 20 30.4 Res 5... 59.0 34 35 26 17.6 36. 4' 44. 0 v 49 54 52. 0 Ductill at 77 ove 150 76 100 12 5.1 P. I 1.6 0.0 -0.s 3.5 4.1 Melting Point, 0 5s 57 56 89 Those versed in the art will note in the above table that the gel type shows a very low ductility with a generally relatively high 'asphaltene content in proportion to the resin content.

The gel asphalts also lack a coherent fluidity at the" melting point; instead they show a stiff plastic structure which is often found to be of a friable nature in the cold.

Asphalt technologists use the ductility test as an indicator of good adhesion. However, I use the ductility test as a measure to indicate how well the hydrocarbons Patented May 27, 1958- In sum-- the penetration index (P. 1;).

formation of organic acid by oxidation.

. o a p a 7 are dispersedfinone another, a low ductility test indicating at once an unstable condition in the bitumen and this is directly related to adhesiveness.

' As seen from the above table, we have a low penetration index for a sql type aspha-lt' high in ductility an average-Mexican and straight fr'un Venezuelan asphalt in short which prevents bitumen deterioration in asphalt pavements and asphalt roofs on. exposure to the elements over long periods of time, is an aromatic 011, containing highboiling alkylated cresols and to a lesser extent the guaiacols, condensed aromatics, etc, and known in com- J merce'as pine tar of medium and heavy grade.

shoWing- 0.8 to 0.0 penetration i-ndex hence good cluction done at 77fas form'ulated by Pfeilier and Van Doormal--(Proceedings International Association of Testing Materials, London, Cong. 1937, page 504).

A high concentration of asphaltenes to resins gives a high penetration index. IA 'zero penetration index indie catesa well balanced adhesiveasphal't, which maybe as low as .-'1 oi l. 8-or thereabout. A high penetration index such as 2.0, 3.0 .or over indicates an oxidized material-or blown? asphalts of high asphaltcne content,

, reducedresin content, low ductility and lack of adhesivity.

' To relatethe tendency of bitumens to age on the road to a laboratory accelerated ageing test, I employ'a test called, thin-film ageing test. This laboratory test which is simple toperform is that describedby Pauls and Welborn, Public Roads, vol. 27, No. 9,August 1953. In this test 50 milliliters of sample are exposed in flat tins or containers of 5.5 inches in diameter at a bitumen depth of about 1 5 inch for periods of 5, 8, 12 or 24. hours depending upon how drastic the test is to be;

fIn this thin film ageing testthe asphalt is heated in a controlled electrically heated oven with free access of air at 325 9 F. and is made of the two constants of an asphalt, namely the penetration index at 77. F. and the ductility at 77 F. Todetermine the penetration index'by Van Doormals method, I determine the penetration at'r77 F. and the meltingpoint and calculate A Mexican soft asphalt will show a zeropenetration index, blown asphalts over 1.0 to about 7 to 8, suspectible asphalts below 0, and cracked asphalts and coal tarv pitches below 1 to as low as '4 or 5.

' It is one of my objects to prevent the bitumenin a pavement, for example, for oxidizingover a period of years. r a

It is alsomy objective to add to the'asphalt, prior to 15 a a a Medium Pine Heavy Pine Tar, Tar, i. e. type K i. e. type L Speeific Grav'lty at 15 0 1075-1080. 7

9 Moisture Content Trace.

Flash Point (Open Cup) 2579 265 F;

Acidity (As Acetic Acid)-- 0.1% 0.1% Maximum; Viscosity (Stormer 0.)... 6-10 Mine, 150 16-20 Mme, 150

Grams. 60Grams. Acid Number--.

olor Golden Brown. Solubility in'Benzol 99.5%.

. Medium 7 Specific gravity atil5.5/l5.l5 C 1.056. 40 Absolute viscosity ceniipoises at 30 C- 2100.

Acid number -a S1. Moisturern Not more thanpine tars are free of suspended carbon and contain large amounts of aromatics and polar compounds and theyare 100 percent soluble in alcohol.

In addi tion these pine tar products contain terpenes of high solventpower,

capable of exerting" anti-oxidant action.

resin acids and fluid terpene pitch-like. condensates 7 Pine tar has the following established specification: i

Pounds per gallon (15 0.);

8 Gals. in 100 pounds (15 G.)

Representative Distillation:

-Another type of pine tar (type M) commercially available in medium to. extra heavy grades and which- Ixuse has the following characteristics.

Flash point (open cup);

2% by vlclu me.

' Ash 0.1%.

. Distillation, A. 8. T. M. D20-30 appa- V f ratus: V V I 1 5%- volume 222 C. 10% volume 1 238C. 50% volume 338C.

' volume- 352 C.

% volume a 1 the start of the deterioration action of the elements, a e

substance that will hinder to a great extent the increase in asphalt'ene concentration as evidenced by a highP.-I." and by low ductility. The lattertwo' properties go hand in hand though. I prefer to. consider the ductility of an asphaltto befa more sensitive indicator of deep seated degradation changes going on in a-bitumen-.- ,It is also my objective to supply to the bitumena solubilizerfor maintaining or for restoring the peptizingto a high degree ofdispersion.

It is also my objective to simultaneously siipplyto the asphalt composition an anti-oxidant -to act'upon the oily constituents of the bitumen; i. el'the naphthenic. and parafiinic hydrocarbons.. My" anti-oxidants prevent These acids are 7 oil solubleelectrolytes andact as precipitants to the asphaltenes tending to yield coarse or unstable asphaltene dispersions in the acidic composition. I The material I have discovered which preventsto a large degree this oxidatiomi. e. a'sphaltene increase as action of the resinsiand for'solubilizing the enhances? Coffefation of thin film oven test with road record of extracted bitumens.-R. Vokac, at the Montana National Bituminous Conference, September 1939, gave tests on extracted asphalts from pavements up to, '14. years old 1 Lewis (Accelerated Durability Testing of Bituminous Material, 52nd annual meetings, A. S. T. M., July 1949,

evidenced by high penetration index and 'low ductility, 75 Spec. Tech. Public-"No. 94,; page .35), indicates that the These 7 hour thin film test at 325 F. coincides with tests of an extracted bitumen from road ways of about years old:

Pent., Duct., F., P. I 77 F. 77 F. M. P.

Cm. 7 hr. Thin Film Test as" thlck).- 28 14 150.9 0.9 Extracted asphalt from 10 year pavement 27 149 0.7

i. e. (B). The physical constants of these asphalts are:

96. Melting Point (R 8: B 120 F. Ductility at 77 F 100 plus cm. Soluble in (So 9 91 99.98%. Flash point, open mn 520 F. Penetration Index (Shell Method) -0.8 0.2.

In order to simulate the results of the Lewis values in the seven hour accelerated durability test described above, some of my asphalt compositions were exposed for eight hours at 325 F. in the Vs inch film thickness test instead of for seven hours. This procedure made the test more severe than that of the seven hour Lewis method.

In the case of asphalt B the thin film test was run for 10 hours at 325 F. in order to obtain an appreciable hardening eifect.

In Tables 11 and HI below my composition blends are shown using asphalt A and B respectively and the pine tar types described above.

TABLE II Eight hour thin film test at 325 F. with asphalt A Pine Tar Additive Type Type Type K L M Percentage added" none 1 1. 75 0. 75 Penet. at 77 33 88 38 36 M. P. (R. & B.) F 154 144 145 142 Penetration Index (Shell) 1. 5 0.8 0.9 0. 1 Ductility, 77 F em 18 33 57 42 Penet. at 77 F. Before running the Eight hour Test 76 82 78 100 TABLE III Ten hour thin film test at 325 F. with asphalt B Pine Tar Additive, Type K L none 1.0 0.75 1. 5 53 52 54 61 142 137 134 130 1. 4 0.8 0. 6 0. 4 36 65 60 75 Pent. before Test 96 100 100 106 It is seen from Tables 11 and III above that high boilings pine tar oils exert a marked anti-deterioration efiect on these two asphalt: used in industry.

The effect of pine tar addition is most marked in the solubilizing power of the pine tar additive on the asphalt hydrocarbons when disturbed by oxidation. This oxidation normally produces a low ductility material of 18 and 36 cm. respectively for asphalt A and B. But the solubilizing and anti-oxidant eifect of pine tar additions results in an increased and very satisfactory ductility for asphalt A and B compositions containing pine tar. Furthermore a relatively low increase in the melting point over that of the unblended asphalt at a given penetration is obtained, again indicating less disturbance by oxidation of the asphaltene dispersion in the asphalt thereby producing a more homogeneous and longer life asphalt. For instance where asphalt A and B would normally show signs of cracking in a ten to twenty year period in the pavement, the addition of pine tars greatly increases the pavement life-span from two to three fold.

learly this invention is of a generic nature and is not to be limited to the pine tars used for illustrative purposes, nor is it to be limited by any theory. What is certain is that the addition of pine tars to asphalts yields compositions which have much longer useful lives than asphalts having no pine tar therein, thereby maintaining the new asphalt compositions in substantially their original physical condition for a much longer time than when no pine tar is added to the asphalt or bitumen. Bitumen is but another name for asphalt.

The amount of pine tar useable is 0.1 to 5.0 percent or more but preferred results are obtained with asphalt composition containing from 0.5 to 1.5 percent pine tar. And while pine tars are preferred, other wood tars, for example from the wood distillation industry or tars from the coal tar industry are operable.

The asphalts useable are preferably obtained from the petroleum industry, but asphalts and bitumens obtained from other sources are also operable.

In the making of asphalt roads on the average about 10 percent asphalt is used with about percent sand and/or aggregate. However, this amount may vary somewhat from the average value of 10 percent depending on the location of the road, weight of trafiic, etc.

In the preparation of roofing material, the web of cellulosic or other fibers is saturated with the inventive asphalt composition containing pine tar.

I claim:

1. A non-brittle, non-lustrous, oxidation resistant asphalt composition of matter for road paving capable of solubilizing asphaltenes as they are formed comprising asphalt and 0.1 to 5 .0 percent by weight of alcohol soluble pine tar containing substantially no free carbon.

2. The composition of claim 1 wherein the amount of pin tar varies from 0.5 to 1.5 percent by weight.

References Cited in the file of this patent UNITED STATES PATENTS 564,975 Dean Aug. 4, 1896 569,854 Cotter et al Oct. 20, 1896 1,492,408 Ullrich Apr. 29, 1924 1,603,502 Alexander Oct. 19, 1926 1,972,055 Richter Aug. 29, 1934 2,427,488 Anderson et al Sept. 16, 1947 FOREIGN PATENTS 23,981 Great Britain of 1895 577,639 France Sept. 8, 1924 OTHER REFERENCES Abraham Asphalt and Allied Substances, 5th ed. 1945,

pp. 326-328, 580-581, and chart between 2 p. 

1. A NON-BRITTLE, NON-LUSTROUS, OXIDATION RESISTANT ASPHALT COMPOSITION OF MATTER FOR ORAD PAVING CAPABLE OF SOLUBILIZING ASPHALTENES AS THEY ARE FORMED COMPRISING ASPHALT AND 0.1 TO 5.0 PERCENT BY WEIGHT OF ALCOHOL SOLUBLE PINE TAR CONTAINING SUBSTANTIALLY NO FREE CARBON. 